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CN-121975431-A - Biphase hybridization anti-icing coating, preparation method and application thereof

CN121975431ACN 121975431 ACN121975431 ACN 121975431ACN-121975431-A

Abstract

The invention relates to the technical field of functional coating materials, in particular to a biphase hybridization anti-icing coating, a preparation method and application thereof. The biphase hybridization anti-icing coating comprises a hydrophobic phase base material and an enhancement phase base material, wherein the hydrophobic phase base material is formed by compounding surface modified nano silicon dioxide and PDMS, and the enhancement phase base material is formed by compounding COF and graphene. The PDMS with low surface energy and the modified nano silicon dioxide are mixed to form a hydrophobic phase base material, the graphene with good mechanical strength and photo-thermal electric effect and the COF material are mixed to form a reinforced phase base material, and the reinforced phase base material is mixed in two phases and subjected to plasma pretreatment, a coating process and temperature and humidity control post-treatment to form a uniform biphase hybridization anti-icing coating, so that the modified nano silicon dioxide anti-icing coating can be used for anti-icing protection of fuel cell parts.

Inventors

  • SONG YARU
  • FU PENG
  • ZHANG SHAOJIE
  • WU GUOLING
  • WAN TIANHUA
  • JIA BAOJUAN

Assignees

  • 山东国创燃料电池技术创新中心有限公司

Dates

Publication Date
20260505
Application Date
20260409

Claims (10)

  1. 1. A dual-phase hybrid anti-icing coating, characterized in that the dual-phase hybrid anti-icing coating comprises a hydrophobic phase binder and an enhancement phase binder; The hydrophobic phase base material is formed by compounding surface modified nano silicon dioxide and PDMS, and the reinforcing phase base material is formed by compounding COF and graphene; the surface modified nano silicon dioxide modifier is a silane coupling agent, wherein the silane coupling agent is at least one of KH-550, KH-570 or perfluorooctyl triethoxysilane; The mass ratio of the nano silicon dioxide to the silane coupling agent is 10:1-5:1; The mass ratio of the hydrophobic phase base material to the reinforcing phase base material is 50:1-10:1.
  2. 2. The dual-phase hybrid anti-icing coating according to claim 1, characterized in that the mass ratio of surface-modified nanosilica to PDMS is 1:20-3:4; or, the COF is at least one of COF-366, TP-COF, DAAQ-TFP COF and COF-JLU.
  3. 3. The dual-phase hybrid anti-icing coating according to claim 1, wherein the mass ratio of COF to graphene is 4:1-1:1.
  4. 4. The dual-phase hybrid anti-icing coating according to claim 1, characterized in that the thickness of the dual-phase hybrid anti-icing coating is 10-50 μm.
  5. 5. The method for preparing a dual-phase hybrid anti-icing coating according to claim 1, comprising the steps of: Preparing a hydrophobic phase base stock dispersion liquid: Mixing a silane coupling agent and nano silicon dioxide in an organic solvent 1, heating, stirring, centrifugally separating a solid product, washing and drying to obtain surface modified nano silicon dioxide; mixing the surface modified nano silicon dioxide with an organic solvent 2 to obtain a dispersion liquid A; dissolving PDMS prepolymer in an organic solvent 3, mixing with the dispersion liquid A, and stirring to form hydrophobic phase base stock dispersion liquid; Preparing reinforcing phase base stock dispersion liquid: synthesizing the COF by adopting a solvothermal method; Ultrasonically dispersing the COF and the graphene in an organic solvent 4 to form a reinforcing phase base stock dispersion liquid; Preparing a biphase hybridization anti-icing coating: Mixing the hydrophobic phase base stock dispersion liquid with the reinforcing phase base stock dispersion liquid, and dispersing to obtain coating slurry; And (3) carrying out plasma surface treatment on the substrate, coating slurry on the surface of the substrate, and carrying out temperature and humidity control post-treatment to obtain the biphase hybridization anti-icing coating.
  6. 6. The method according to claim 5, wherein in the step of preparing the hydrophobic phase base dispersion, the nano silica has a particle size of 30-60 nm, and the silane coupling agent is at least one of KH-550, KH-570 or perfluorooctyl triethoxysilane; or the mass ratio of the nano silicon dioxide to the coupling agent is 10:1-5:1; Or, the organic solvent 1 is selected from one or more of ethanol, isopropanol, acetone, toluene, xylene, n-hexane, tetrahydrofuran, chloroform and water; Or mixing the silane coupling agent and the nano silicon dioxide, heating to 60-80 ℃, stirring for 2-4 hours, and vacuum drying at 60-80 ℃ for 12-24 hours.
  7. 7. The method according to claim 5, wherein in the step of preparing the hydrophobic phase base dispersion, the organic solvent 2 is one or more selected from toluene, xylene, n-hexane, and tetrahydrofuran; Or, in the dispersion liquid A, the mass fraction of the surface modified nano silicon dioxide is 5-15 wt%; or mixing the surface modified nano silicon dioxide with the organic solvent 2, and then carrying out high-speed shearing or ultrasonic treatment, wherein the rotating speed of the high-speed shearing is 10000-20000 rpm, the time is 20-30 minutes, the power of ultrasonic treatment is 300-800W, and the time is 40-60 minutes; Or, in the preparation step of the hydrophobic phase base stock dispersion liquid, the organic solvent 3 is one or more of toluene, xylene, n-hexane and tetrahydrofuran; Or, after dissolving PDMS prepolymer in organic solvent 3, mixing with dispersion A according to the mass ratio of 1:1-5:1.
  8. 8. The method of claim 5 wherein in the step of formulating the reinforcing phase binder dispersion, the COF is at least one of COF-366, TP-COF, DAAQ-TFP COF, COF-JLU; Or the organic solvent 4 is one or more of N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide and tetrahydrofuran, wherein the mass ratio of COF to graphene is 4:1-1:1; or, in the step of preparing the reinforcing phase base stock dispersion liquid, the ultrasonic power is 300-800W, and the time is 2-3 hours.
  9. 9. The process according to claim 5, wherein in the step of preparing the biphasic hybrid anti-icing coating, the volume ratio of the hydrophobic phase base dispersion to the reinforcing phase base dispersion is 9:1 to 1:1, the dispersing process is selected from the group consisting of magnetic stirring, ultrasonic dispersing, ball milling, high-pressure homogenization and microfluidization, Or, in the preparation step of the biphase hybridization anti-icing coating, the plasma surface treatment is oxygen plasma oxidation treatment, the power is 20-100W, the time is 1-10 minutes, the gas flow is 5-100 sccm, and the gas pressure is 10-100 m Torr; or, in the two-phase hybrid anti-icing coating preparation step, the coating method is selected from spraying, spin coating, blade coating or ink-jet printing; Or, in the preparation step of the biphase hybrid anti-icing coating, the temperature and humidity control post-treatment comprises 3 stages, wherein stage 1 is low-temperature low-humidity pre-curing 0.5-1 h, the temperature is 60 ℃ plus or minus 2 ℃, the humidity is 30% RH plus or minus 5%, stage 2 is middle-temperature middle-humidity interface strengthening 1-3 h, the temperature is 70 ℃ plus or minus 2 ℃ to 80 ℃ plus or minus 2 ℃, the humidity is 50% RH plus or minus 5%, and stage 3 is naturally cooled and stable, and the humidity is the same as the ambient humidity; Alternatively, the thickness of the biphasic hybrid anti-icing coating is 10-50 μm.
  10. 10. Use of the dual-phase hybrid anti-icing coating according to any of claims 1-4 for anti-icing protection of fuel cell external components.

Description

Biphase hybridization anti-icing coating, preparation method and application thereof Technical Field The invention relates to the technical field of functional coating materials, in particular to a biphase hybridization anti-icing coating, a preparation method and application thereof. Background Once the air temperature is lower than the freezing point, the electric pile of the system core part of the fuel cell is frozen in a straight surface, and once the catalyst and the proton exchange membrane on the membrane electrode of the electric pile are covered by ice, the starting reaction performance of the fuel cell is directly affected. If the freezing condition is severe, the fuel cell can even fail to react at all and cause irrecoverable damage to the membrane electrode. The mode of realizing hydrophobic and anti-icing in the prior art mainly comprises a graphene oxide/epoxy resin system, a CuO-MWCNTs composite structure and a PDMS/nano silver graphene material compounding or surface microstructure design, but the prior art focuses on single function realization, such as simple hydrophobic, photo-thermal effect or mechanical enhancement, and has insufficient adaptability to complex working conditions. Disclosure of Invention In view of the above, the invention provides a biphase hybridization anti-icing coating, a preparation method and application thereof. The invention realizes the multifunctional coupling of hydrophobic, mechanical enhancement and light/electric heat through the synergy of the hydrophobic phase base material and the enhancement phase base material and the plasma pretreatment and the temperature and humidity control post-treatment, and breaks through the contradiction between the mechanical property and the functionality of the traditional homogeneous coating. In order to achieve the above object, the present invention is realized by the following technical scheme: In a first aspect, the present invention provides a dual-phase hybrid anti-icing coating comprising a hydrophobic phase binder and an enhancement phase binder; The hydrophobic phase base material is formed by compounding surface modified nano silicon dioxide and PDMS, and the reinforcing phase base material is formed by compounding COF and graphene. Further, the surface modified nano silicon dioxide modifier is a silane coupling agent, wherein the silane coupling agent is at least one of KH-550 (aminosilane), KH-570 (methacryloxy silane) or perfluorooctyl triethoxy silane. Further, the mass ratio of the nano silicon dioxide to the coupling agent is 10:1-5:1. Further, the mass ratio of the surface modified nano silicon dioxide to the PDMS is 1:20-3:4. Further, the COF is at least one of COF-366, TP-COF, DAAQ-TFP COF and COF-JLU. Further, COF-366 was synthesized from 5,10,15, 20-tetra (4-aminophenyl) porphyrin (TAPP) and 1,3, 5-Trimethylbenzene (TFB), TP-COF was synthesized from (1, 3, 5-tris (4-aminophenyl) benzene (TAPB) and 2, 5-dimethoxy terephthalaldehyde (DMTA), DAAQ-TFP COF was synthesized from 2, 6-Diaminoanthraquinone (DAAQ) and 1,3, 5-Trimethylphloroglucinol (TFP), and COF-JLU13 was synthesized from 4,4' ' - (benzo [1,2-b:4,5-b ' ] dithiophene-2, 6-diyl) triphenylamine (BDT-TPA) and 1,3, 5-tris (4-formylphenyl) benzene (TFPT). Further, the mass ratio of the COF to the graphene is 4:1-1:1. Further, the mass ratio of the hydrophobic phase binder to the reinforcing phase binder is 50:1 to 10:1, preferably 35:1 to 20:1. Further, the thickness of the biphase hybrid anti-icing coating is 10-50 μm. In a second aspect, the present invention provides a method for preparing the biphase hybridization anti-icing coating according to the first aspect, comprising the following steps: Preparing a hydrophobic phase base stock dispersion liquid: Mixing a silane coupling agent and nano silicon dioxide in an organic solvent 1, heating, stirring, centrifugally separating a solid product, washing and drying to obtain surface modified nano silicon dioxide; mixing the surface modified nano silicon dioxide with an organic solvent 2 to obtain a dispersion liquid A; dissolving PDMS prepolymer in an organic solvent 3, mixing with the dispersion liquid A, and stirring to form hydrophobic phase base stock dispersion liquid; Preparing reinforcing phase base stock dispersion liquid: synthesizing the COF by adopting a solvothermal method; Ultrasonically dispersing the COF and the graphene in an organic solvent 4 to form a reinforcing phase base stock dispersion liquid; Preparing a biphase hybridization anti-icing coating: Mixing the hydrophobic phase base stock dispersion liquid with the reinforcing phase base stock dispersion liquid, and dispersing to obtain coating slurry; And (3) carrying out plasma surface treatment on the substrate, coating slurry on the surface of the substrate, and carrying out temperature and humidity control post-treatment to obtain the biphase hybridization anti-icing coating. Further, in the preparation step of the hydropho